Disperse dyes, their preparation and their use

ABSTRACT

The present invention provides dyes of the general formula (I) where D, R1 to R7 and n are each as defined in claim 1, processes for their preparation and their use.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C. §371)of PCT/EP2007/061002, filed Oct. 16, 2007, which claims benefit ofGerman application 10 2006 050642.1, filed Oct. 27, 2006.

BACKGROUND OF THE INVENTION

The present invention relates to disperse azo dyes in which a 2-oxoalkylester is linked to the chromophore. Dyes having this structural elementare already known and described for example in GB 909843, WO95/20014 andWO05/056690. It has now been found that disperse azo dyes in which thestructural element in question is linked to further selected structuralelements in a certain manner have excellent properties and providedyeings having excellent wash fastnesses and very good sublimationfastnesses.

BRIEF SUMMARY OF THE INVENTION

The invention relates to a dye of the formula (I)

where

-   D is the radical of a diazo component;-   R¹ is hydrogen, (C₁-C₆)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, halogen,    —NHCHO, —NHCO(C₁-C₆)-alkyl, —NHCOaryl, —NHSO₂(C₁-C₆)-alkyl or    —NHSO₂aryl;-   R² is hydrogen, (C₁-C₆)-alkyl, (C₁-C₄)-alkoxy, phenoxy or halogen;-   R³ is hydrogen, (C₁-C₆)-alkyl, substituted (C₁-C₆)-alkyl,    (C₃-C₄)-alkenyl or substituted (C₃-C₄)-alkenyl;    or R² and R³ combine to form the radical —C*H(CH₃)CH₂C(CH₃)₂—, where    the carbon atom marked by * is attached to the phenyl nucleus;-   R⁴ is hydrogen, (C₁-C₆)-alkyl or phenyl;-   R⁵ is (C₁-C₆)-alkyl or substituted (C₁-C₆)-alkyl;-   R⁶ is hydrogen or (C₁-C₆)-alkyl;-   R⁷ is hydrogen, (C₁-C₆)-alkyl or phenyl; and-   n 0, 1, 2 or 3;    although the compounds of the formulae

shall be excluded. The invention also relates to the process to make thedye and the process of using the dye.

DETAILED DESCRIPTION OF THE INVENTION

D radicals of a diazo component are in particular those customary in thefield of disperse dyes and known to one skilled in the art.

Preferably, D represents a group of the formula (IIa)

where

-   T¹ and T² independently are hydrogen, (C₁-C₆)-alkyl, (C₁-C₄)-alkoxy,    —SO₂(C₁-C₆)-alkyl, —SO₂aryl, cyano, halogen or nitro; and-   T⁴ and T³ independently are hydrogen, halogen, trifluoromethyl,    cyano, —SCN, —SO₂CH₃ or nitro;    although at least one of T¹, T², T³ and T⁴ is not hydrogen;    or represents a group of the formula (IIb)

where

-   T⁵ and T^(5′) independently are hydrogen or halogen; and-   T⁶ is hydrogen, —SO₂CH₃, —SCN, (C₁-C₄)-alkoxy, halogen or nitro;    although at least one of T⁵, T^(5′) and T⁶ is not hydrogen;    or represents a group of the formula (IIc)

where

-   T¹² is hydrogen or halogen;    or represents a group of the formula (IId)

where

-   T⁷ is nitro, —CHO, cyano, —COCH₃ or a group of the formula

-   where T¹⁰ is hydrogen, halogen, nitro or cyano;-   T⁸ is hydrogen, (C₁-C₆)-alkyl or halogen; and-   T⁹ is nitro, cyano, —COCH₃ or —COOT¹¹; where T¹¹ is (C₁-C₄)-alkyl;    or represents a group of the formula (IIe)

where T⁷ and T⁸ are each as defined above;or represents a group of the formula (IIf)

where T¹³ is phenyl or S—(C₁-C₄)-alkyl.

(C₁-C₆)-Alkyl groups may be straight chain or branched and are, forexample, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl,tert-butyl, n-pentyl or n-hexyl. A similar logic applies to alkoxygroups, which are methoxy or ethoxy for example. (C₃-C₄)-Alkenyl groupsare in particular allyl.

Substituted (C₁-C₆)-alkyl and (C₃-C₄)-alkenyl groups are in particularsubstituted by 1 to 3 substituents from the group consisting of halogen,cyano, hydroxyl, (C₁-C₆)-alkoxy, —COO(C₁-C₆)-alkyl, —COOaryl,—OCOO(C₁-C₆)-alkyl, —OCOOaryl, —OCO(C₁-C₆)-alkyl, phenyl, —OCOphenyl andphenoxy.

Aryl is in particular phenyl or naphthyl, —NHSO₂aryl is in particularphenylsulfonylamino. Halogen preferably represents chlorine or bromine.

R¹ is preferably hydrogen, chlorine, methyl, ethyl, hydroxyl, methoxy,ethoxy, acetylamino, propionylamino, benzoylamino, methylsulfonylamino,ethylsulfonylamino or phenylsulfonylamino.

R² is preferably hydrogen, chlorine, methyl, ethyl, methoxy, ethoxy orphenoxy.

R³ is preferably hydrogen, methyl, ethyl, propyl, butyl, benzyl,phenylethyl, phenoxyethyl, methoxyethyl, cyanoethyl, —C₂H₄OCOCH₃,—C₂H₄OCOC₂H₅, —C₂H₄COOCH₃, —C₂H₄COOC₂H₅ or allyl.

R⁴ and R⁷ are each preferably hydrogen, methyl or phenyl, morepreferably hydrogen. R⁶ is preferably hydrogen or methyl.

R⁵ is preferably methyl or ethyl.

n is preferably 0 or 1, more preferably 0.

Preferred dyes according to the present invention conform to the generalformula (Ia)

where T¹ to T⁴, R¹ to R⁷ and n are each as defined above, but thecompounds of the formulae

shall be excluded.

In preferred dyes of the general formula (Ia), R³ is not ethyl when R¹is hydrogen and n=0. In further preferred dyes of the general formula(Ia), R³ is not n-propyl or n-butyl when R¹ is —NHCOCH₃ and n=0.

In particularly preferred dyes of the general formula (Ia),

-   R¹ is acetylamino, propionylamino, benzoylamino or    methylsulfonylamino;-   R² is hydrogen, chlorine, methoxy or ethoxy;-   R³ is hydrogen, methyl, ethyl, allyl or benzyl;-   R⁴ is hydrogen or methyl;-   R⁵ methyl or ethyl;-   R⁶ is hydrogen or methyl and-   R⁷ is hydrogen, methyl or phenyl.

Particularly preferred dyes of the general formula (Ia) according to thepresent invention conform to the general formula (Iaa)

where

-   T¹ is hydrogen, nitro or methyl;-   T² is hydrogen, nitro or chlorine;-   T³ is hydrogen, cyano, chlorine or bromine;-   T⁴ is hydrogen, cyano, nitro, chlorine, bromine or trifluoromethyl;-   R¹ is hydrogen, hydroxyl, chlorine, methyl, acetylamino,    propionylamino, benzoylamino or methylsulfonylamino;-   R² is hydrogen, chlorine, methyl, phenoxy, methoxy or ethoxy;-   R³ is hydrogen, methyl, ethyl, butyl, benzyl, phenylethyl,    phenoxyethyl or allyl;-   R⁵ is methyl or ethyl; and-   R⁴ and R⁷ are hydrogen, methyl or phenyl;    although the compounds of the formulae

shall be excluded.

In preferred dyes of the general formula (Iaa), R³ is not ethyl when R¹is hydrogen. In further preferred dyes of the general formula (Ia), R³is not n-propyl or n-butyl when R¹ is —NHCOCH₃.

Further preferred dyes according to the present invention conform to thegeneral formula (Ib)

where T¹², R¹ to R⁷ and n are each as defined above.

Particularly preferred dyes of this type according to the presentinvention conform to the general formula (Iba)

where

-   T¹² is hydrogen, chlorine or bromine;-   R¹ is hydrogen, hydroxyl, methyl, acetylamino or propionylamino;-   R² is hydrogen, methyl, chlorine or methoxy;-   R³ is hydrogen, ethyl, butyl, benzyl or allyl; and-   R⁵ is methyl or ethyl.

Further preferred dyes according to the present invention conform to thegeneral formula (Ic)

where T⁵, T^(5′), T⁶, R¹ to R⁷ and n are each as defined above.

Particularly preferred dyes of this type according to the presentinvention conform to the general formula (Ica)

where

-   T⁵ and T^(5′) independently are hydrogen or halogen;-   T⁶ is halogen or nitro;-   R¹ is hydrogen, hydroxyl, methyl, acetylamino or propionylamino;-   R² is hydrogen, methyl, chlorine or methoxy;-   R³ is hydrogen, ethyl, butyl, benzyl or allyl; and-   R⁵ is methyl or ethyl.

Further preferred dyes according to the present invention conform to thegeneral formula (Id)

where T⁷ to T⁹, R¹ to R⁷ and n are each as defined above.

Particularly preferred dyes of this type according to the presentinvention conform to the general formula (Ida)

where

-   T⁷ is nitro, —CHO or cyano;-   T⁸ is hydrogen, methyl or chlorine;-   T⁹ is nitro, cyano or —COCH₃;-   R¹ is hydrogen, hydroxyl, methyl, acetylamino or propionylamino;-   R² is hydrogen, methyl, chlorine or methoxy;-   R³ is hydrogen, methyl, ethyl, butyl, benzyl, phenoxyethyl or allyl;    and-   R⁵ is methyl or ethyl.

Further particularly preferred dyes of this type according to thepresent invention conform to the general formula (Idb)

where

-   T¹⁰ is nitro;-   T⁹ is cyano or —COCH₃;-   ¹ is hydrogen, methyl or acetylamino;-   ³ is methyl, ethyl, butyl or allyl; and-   R⁵ methyl or ethyl.

Further preferred dyes according to the present invention conform to thegeneral formula (Ie)

where T⁷, T⁸, R¹ to R⁷ and n are each as defined above and T⁷ is inparticular nitro, —CHO, COCH₃ or cyano.

Particularly preferred dyes of this type according to the presentinvention conform to the general formula (Iea)

where

-   T⁷ is nitro, —CHO or cyano;-   T⁸ is hydrogen or chlorine;-   R¹ is hydrogen, hydroxyl, methyl, acetylamino or propionylamino;-   R² is hydrogen, methyl, chlorine or methoxy;-   R³ is hydrogen, methyl, ethyl, butyl, benzyl, phenoxyethyl or allyl;    and-   R⁵ is methyl or ethyl.

Further preferred dyes according to the present invention conform to thegeneral formula (If)

where

-   T¹³, R¹ to R⁷ and n are each as defined above.

Particularly preferred dyes of this type according to the presentinvention conform to the general formula (Ifa)

where

-   R¹ is hydrogen, hydroxyl, methyl, acetylamino or propionylamino;-   R² is hydrogen, methyl, chlorine or methoxy;-   R³ is hydrogen, methyl, ethyl, butyl, benzyl, phenoxyethyl or allyl;    and-   R⁵ is methyl or ethyl.

The dyes of the general formula (I) according to the present inventionare obtainable using methods known to one skilled in the art.

For instance, a compound of the general formula (III)D-NH₂  (III)where D is as defined above, is diazotized and coupled onto a compoundof the general formula (IV)

where R¹ to R⁷ and n are each as defined above.

The diazotizing of the compounds of the general formula (III) isgenerally effected in a known manner, for example using sodium nitritein an aqueous medium rendered acidic, for example with hydrochloric orsulfuric acid, or using nitrosylsulfuric acid in dilute sulfuric acid,phosphoric acid or in a mixture of acetic acid and propionic acid. Thepreferred temperature range is between 0° C. and 15° C.

The coupling of the diazotized compounds onto the compounds of thegeneral formula (IV) is generally likewise effected in a known manner,for example in an acidic, aqueous, aqueous-organic or organic medium,particularly advantageously at temperatures below 10° C. Acids used arein particular sulfuric acid, acetic acid or propionic acid.

The compounds of the general formulae (III) and (IV) are known and canbe prepared by known methods.

The present invention's dyes of the general formula (I) are very usefulfor dyeing and printing hydrophobic materials, the dyeings and printsobtained being notable for level hues and high service fastnesses.Deserving of particular mention are excellent wash fastnesses and verygood sublimation fastnesses.

The present invention thus also provides for the use of the dyes of thegeneral formula I for dyeing and printing hydrophobic materials, i.e.,processes for dyeing or printing such materials in a conventional mannerwherein one or more dyes of the general formula (I) according to thepresent invention are used as a colorant.

The hydrophobic materials mentioned may be of synthetic or semisyntheticorigin. Useful hydrophobic materials include for example secondarycellulose acetate, cellulose triacetate, polyamides and, in particular,high molecular weight polyesters. Materials of high molecular weightpolyester are in particular those based on polyethylene glycolterephthalates.

The hydrophobic synthetic materials can be present in the form of sheet-or threadlike constructions and can have been processed, for example,into yarns or into woven or knit textile materials. Preference is givento fibrous textile materials, which may also be present in the form ofmicrofibers for example.

The dyeing in accordance with the use provided by the present inventioncan be carried out in a conventional manner, preferably from an aqueousdispersion, if appropriate in the presence of carriers, at between 80 toabout 110° C. by the exhaust process or by the HT process in a dyeingautoclave at 110 to 140° C., and also by the so-called thermofixprocess, in which the fabric is padded with the dyeing liquor andsubsequently fixed/set at about 180 to 230° C.

Printing of the materials mentioned can be carried out in a manner knownper se by incorporating the dye of the general formula (I) of thepresent invention in a print paste and treating the fabric printedtherewith at temperatures between 180 to 230° C. with HT steam,high-pressure steam or dry heat, if appropriate in the presence of acarrier, to fix the dye.

The dyes of the general formula (I) of the present invention shall be ina very fine state of subdivision when they are used in dyeing liquors,padding liquors or print pastes.

The dyes are converted into the fine state of subdivision in aconventional manner by slurrying the as-fabricated dye together withdispersants in a liquid medium, preferably in water, and subjecting themixture to the action of shearing forces to mechanically comminute theoriginal dye particles to such an extent that an optimal specificsurface area is achieved and sedimentation of the dye is minimized. Thisis accomplished in suitable mills, such as ball or sand mills. Theparticle size of the dyes is generally between 0.5 and 5 μm andpreferably equal to about 1 μm.

The dispersants used in the milling operation can be nonionic oranionic. Nonionic dispersants include for example reaction products ofalkylene oxides, for example ethylene oxide or propylene oxide, withalkylatable compounds, for example fatty alcohols, fatty amines, fattyacids, phenols, alkylphenols and carboxamides. Anionic dispersants arefor example lignosulfonates, alkyl- or alkylarylsulfonates or alkylarylpolyglycol ether sulfates.

The dye preparations thus obtained should be pourable for mostapplications. Accordingly, the dye and dispersant content is limited inthese cases. In general, the dispersions are adjusted to a dye contentup to 50 percent by weight and a dispersant content up to about 25percent by weight. For economic reasons, dye contents are in most casesnot allowed to be below 15 percent by weight. The dispersions may alsocontain still further auxiliaries, for example those which act as anoxidizing agent, for example sodium m-nitrobenzenesulfonate, orfungicidal agents, for example sodium o-phenylphenoxide and sodiumpentachlorophenoxide, and particularly so-called “acid donors”, examplesbeing butyrolactone, monochloroacetamide, sodium chloroacetate, sodiumdichloroacetate, the sodium salt of 3-chloropropionic acid, monosulfateesters such as lauryl sulfate for example, and also sulfuric esters ofethoxylated and propoxylated alcohols, for example butylglycol sulfate.

The dye dispersions thus obtained are very advantageous for making updyeing liquors and print pastes.

There are certain fields of use where powder formulations are preferred.These powders comprise the dye, dispersants and other auxiliaries, forexample wetting, oxidizing, preserving and dustproofing agents and theabovementioned “acid donors”.

A preferred method of making pulverulent preparations of dye consists instripping the above-described liquid dye dispersions of their liquid,for example by vacuum drying, freeze drying, by drying on drum dryers,but preferably by spray drying.

The dyeing liquors are made by diluting the requisite amounts of theabove-described dye formulations with the dyeing medium, preferablywater, such that a liquor ratio of 5:1 to 50:1 is obtained for dyeing.In addition, it is generally customary to include further dyeingauxiliaries, such as dispersing, wetting and fixing auxiliaries, in theliquors. Organic and inorganic acids such as acetic acid, succinic acid,boric acid or phosphoric acid are included to set a pH in the range from4 to 5, preferably 4.5. It is advantageous to buffer the pH setting andto add a sufficient amount of a buffering system. The acetic acid/sodiumacetate system is an example of an advantageous buffering system.

To use the dye or dye mixture in textile printing, the requisite amountsof the abovementioned dye formulations are kneaded in a conventionalmanner together with thickeners, for example alkali metal alginates orthe like, and if appropriate further additives, for example fixationaccelerants, wetting agents and oxidizing agents, to give print pastes.

The present invention also provides inks for digital textile printing bythe ink jet process, comprising a present invention dye of the generalformula (I).

The inks of the present invention are preferably aqueous and compriseone or more of the present invention's dyes of the general formula (I),for example in amounts of 0.1% to 50% by weight, preferably in amountsof 1% to 30% by weight and more preferably in amounts of 1% to 15% byweight based on the total weight of the ink. They further comprise inparticular from 0.1% to 20% by weight of a dispersant. Suitabledispersants are known to one skilled in the art, are commerciallyavailable and include for example sulfonated or sulfomethylated lignins,condensation products of aromatic sulfonic acids and formaldehyde,condensation products of substituted or unsubstituted phenol andformaldehyde, polyacrylates and corresponding copolymers, modifiedpolyurethanes and reaction products of alkylene oxides with alkylatablecompounds, for example fatty alcohols, fatty amines, fatty acids,carboxamides and substituted or unsubstituted phenols.

The inks of the present invention may further comprise customaryadditives, for example viscosity moderators to set viscosities in therange from 1.5 to 40.0 mPas in the temperature range of 20 to 50° C.Preferred inks have a viscosity in the range from 1.5 to 20 mPas andparticularly preferred inks have a viscosity in the range from 1.5 to 15mPas.

Useful viscosity moderators include rheological additives, for examplepolyvinyl-caprolactam, polyvinylpyrrolidone and also their copolymers,polyetherpolyol, associative thickeners, polyureas, sodium alginates,modified galactomannans, polyetherurea, polyurethane and nonioniccellulose ethers.

By way of further additives, the inks of the present invention mayinclude surface-active substances to set surface tensions in the rangefrom 20 to 65 mN/m, which are if appropriate adapted depending on theprocess used (thermal or piezo technology). Useful surface-activesubstances include for example surfactants of any kind, preferablynonionic surfactants, butyldiglycol and 1,2 hexanediol.

The inks may further include customary additives, for example chemicalspecies to inhibit fungal and bacterial growth in amounts from 0.01% to1% by weight based on the total weight of the ink.

The inks of the present invention can be prepared in conventional mannerby mixing the components in water.

EXAMPLE 1

4.6 g of 6-chloro-2,4-dinitroaniline are introduced into a mixture of9.8 ml of sulfuric acid (96%), 0.5 ml of water and 3.5 ml ofnitrosylsulfuric acid (40%) at 30 to 35° C. After 3 hours of stirring at30-35° C., excess nitrite is destroyed with amidosulfonic acid. Thediazonium salt solution thus obtained is expediently added dropwise to amixture of 7.0 g of 2-oxopropyl3-[(5-acetylamino-2-methoxyphenyl)ethylamino]-propionate, 50 ml ofmethanol and 200 g of ice. After stirring for one hour the solids arefiltered off with suction, washed with water and dried to leave 7.3 g ofthe dye of the formula (Iab)

(λ_(max) [DMF]=606 nm), which dyes polyester in blue hues having goodwash and sublimation fastnesses.

EXAMPLE 2

7.5 g of 2-oxopropyl3-{[3-acetylamino-4-(2,6-dibromo-4-nitrophenylazo)phenyl]-ethylamino}propionateand 2.15 g of copper(I) cyanide are stirred in 30 ml ofN-methylpyrrolidone at 80° C. for 4 hours. After cooling, 200 ml ofmethanol and 30 ml of water are added dropwise. The precipitate isfiltered off with suction, washed with 5% hydrochloric acid and waterand dried under reduced pressure to leave 4.9 g of the dye of theformula (Iac)

(λ_(max) [DMF]=612 nm), which dyes polyester in brilliant, blue shadesand has excellent wash and sublimation fastnesses.

EXAMPLE 3

Example 2 is repeated except it proceeds from 2-oxopropyl3-{[3-acetylamino-4-(6-bromo-2,4-dinitrophenylazo)phenyl]ethylamino}propionateand utilizes only one equivalent of copper(I) cyanide. The dye thusobtained has the formula (Iad)

(λ_(max) [DMF]=602 nm) and dyes polyester in brilliant, blue shades andgives excellent wash and sublimation fastnesses.

Examples 4 to 145 of Table 1 were prepared in a similar manner.

TABLE 1

λ_(max) Exam- (nm) ple T¹ T² T³ T⁴ R¹ R² R³ R⁵ R⁴ R⁶ R⁷ n DMF 4 NO₂ H BrNO₂ NHCOCH₃ OCH₃ CH₂CH₃ CH₃ H H H 0 604 5 NO₂ H H NO₂ NHCOCH₃ OCH₃CH₂CH₃ CH₃ H H H 0 582 6 NO₂ H Br CN NHCOCH₃ OCH₃ CH₂CH₃ CH₃ H H H 0 6327 NO₂ H Cl NO₂ NHCOCH₃ OCH₃ CH₂CH₃ C₂H₅ H H H 0 604 8 NO₂ H Br NO₂NHCOCH₃ OCH₃ CH₂CH₃ C₂H₅ H H H 0 604 9 NO₂ H H NO₂ NHCOCH₃ OCH₃ CH₂CH₃C₂H₅ H H H 0 582 10 NO₂ H Cl NO₂ NHCOCH₃ OCH₃ CH₃ CH₃ H H H 0 600 11 NO₂H Br NO₂ NHCOCH₃ OCH₃ CH₃ CH₃ H H H 0 598 12 NO₂ H H NO₂ NHCOCH₃ OCH₃CH₃ CH₃ H H H 0 572 13 NO₂ H Cl NO₂ NHCOCH₃ OCH₃ CH₂CH═CH₂ CH₃ H H H 0598 14 NO₂ H Br NO₂ NHCOCH₃ OCH₃ CH₂CH═CH₂ CH₃ H H H 0 598 15 NO₂ H HNO₂ NHCOCH₃ OCH₃ CH₂CH═CH₂ CH₃ H H H 0 574 16 NO₂ H Cl NO₂ NHCOCH₃ OCH₃CH₂C₆H₅ CH₃ H H H 0 590 17 NO₂ H Br NO₂ NHCOCH₃ OCH₃ CH₂C₆H₅ CH₃ H H H 0590 18 NO₂ H H NO₂ NHCOCH₃ OCH₃ CH₂C₆H₅ CH₃ H H H 0 570 19 NO₂ H CN NO₂NHCOCH₃ OCH₃ CH₂C₆H₅ CH₃ H H H 0 634 20 NO₂ H Cl NO₂ NHCOCH₃ OCH₃ H CH₃H H H 0 592 21 NO₂ H Cl NO₂ NHCOCH₃ OC₂H₅ H CH₃ H H H 0 594 22 NO₂ H BrNO₂ NHCOCH₃ OCH₃ H CH₃ H H H 0 594 23 NO₂ H Br NO₂ NHCOCH₃ OCH₃ H C₂H₅ HH H 0 594 24 NO₂ H Cl NO₂ NHCOCH₃ OCH₃ H C₂H₅ H H H 0 600 25 NO₂ H H NO₂NHCOCH₃ OCH₃ H C₂H₅ H H H 0 574 26 NO₂ H H NO₂ NHCOCH₃ OCH₃ H CH₃ H H H0 574 27 NO₂ H H CF₃ NHCOCH₃ OCH₃ H CH₃ H H H 0 542 28 NO₂ H Br CNNHCOCH₃ OCH₃ H CH₃ H H H 0 624 29 NO₂ H Br CF₃ NHCOCH₃ OCH₃ H CH₃ H H H0 562 30 NO₂ H Br NO₂ NHCOC₂H₅ OCH₃ H CH₃ H H H 0 596 31 NO₂ H Cl NO₂NHCOC₂H₅ OCH₃ H CH₃ H H H 0 596 32 NO₂ H H NO₂ NHCOC₂H₅ OCH₃ H CH₃ H H H0 576 33 NO₂ H Br NO₂ NHCOC₆H₅ OCH₃ H CH₃ H H H 0 586 34 NO₂ H Cl NO₂NHCOC₆H₅ OCH₃ H CH₃ H H H 0 586 35 NO₂ H H NO₂ NHCOC₆H₅ OCH₃ H CH₃ H H H0 572 36 NO₂ Cl H NO₂ NHCOCH₃ OCH₃ H CH₃ H H H 0 576 37 NO₂ H Br NO₂NHCOC₆H₅ OCH₃ CH₂CH₃ CH₃ H H H 0 596 38 NO₂ H Br NO₂ NHCOC₂H₅ OCH₃CH₂CH₃ CH₃ H H H 0 606 39 NO₂ H Cl NO₂ NNCOC₂H₅ OCH₃ CH₂CH₃ CH₃ H H H 0608 40 NO₂ H CN NO₂ NHCOCH₃ OCH₃ CH₂CH₃ CH₃ H H H 0 648 41 NO₂ H Br NO₂NHCOC₆H₅ H CH₂CH₃ CH₃ H H H 0 560 42 NO₂ H Br NO₂ NHCOC₂H₅ H CH₂CH₃ CH₃H H H 0 558 43 NO₂ Cl H NO₂ NHCOCH₃ H CH₂CH₃ CH₃ H H H 0 548 44 NO₂ H ClNO₂ NHCOCH₃ H CH₂CH₃ CH₃ H H H 0 560 45 NO₂ H Cl NO₂ NHCOCH₃ H CH₂CH₃C₂H₅ H H H 0 560 46 NO₂ H Br NO₂ NHCOCH₃ H CH₂CH₃ CH₃ H H H 0 558 47 NO₂H Cl NO₂ NHCOCH₃ H n-C₄H₉ CH₃ H H H 0 562 48 NO₂ H Cl H NHCOCH₃ H n-C₄H₉CH₃ H H H 0 534 49 NO₂ H H H NHCOCH₃ H n-C₄H₉ CH₃ H H H 0 516 50 NO₂ HBr CN NHCOCH₃ H n-C₄H₉ CH₃ H H H 0 584 51 NO₂ H CN NO₂ NHCOCH₃ H n-C₄H₉CH₃ H H H 0 604 52 NO₂ H H NO₂ NHCOCH₃ H CH₂CH₃ CH₃ H H H 0 548 53 NO₂ HH CN NHCOCH₃ H CH₂CH₃ CH₃ H H H 0 552 54 NO₂ H Br CN NHCOCH₃ H CH₂CH₃CH₃ H H H 0 582 55 NO₂ H Cl CN NHCOCH₃ H CH₂CH₃ CH₃ H H H 0 582 56 NO₂ HCl H NHCOCH₃ H CH₂CH₃ CH₃ H H H 0 534 57 NO₂ H Br H NHCOCH₃ H CH₂CH₃ CH₃H H H 0 530 58 NO₂ H H H NHCOCH₃ H CH₂CH₃ CH₃ H H H 0 514 59 NO₂ H ClNO₂ NHCOCH₃ H CH₂C₆H₅ CH₃ H H H 0 554 60 NO₂ H H CN NHCOCH₃ H CH₂C₆H₅CH₃ H H H 0 546 61 NO₂ H Br NO₂ NHCOCH₃ H CH₂C₆H₅ CH₃ H H H 0 552 62 NO₂H Cl H NHCOCH₃ H CH₂C₆H₅ CH₃ H H H 0 524 63 NO₂ H H NO₂ NHCOCH₃ HCH₂C₆H₅ CH₃ H H H 0 540 64 NO₂ H H H NHCOCH₃ H CH₂C₆H₅ CH₃ H H H 0 50665 H Cl H Cl NHCOCH₃ H CH₂C₆H₅ CH₃ H H H 0 476 66 NO₂ H Br CN NHCOCH₃ HCH₂C₆H₅ CH₃ H H H 0 574 67 NO₂ H H CN NHCOCH₃ H n-C₄H₉ CH₃ H H H 0 55468 NO₂ H Cl NO₂ NHCOCH₃ H CH₂CH═CH₂ CH₃ H H H 0 556 69 NO₂ H H CNNHCOCH₃ H CH₂CH═CH₂ CH₃ H H H 0 548 70 NO₂ H H Cl NHSO₂CH₃ H CH₂C₆H₅ CH₃H H H 0 534 71 NO₂ H H H NHSO₂CH₃ H CH₂C₆H₅ CH₃ H H H 0 494 72 NO₂ H HCN CH₃ H CH₂CH₃ CH₃ H H H 0 548 73 NO₂ H H CN CH₃ H n-C₄H₉ CH₃ H H H 0550 74 NO₂ H H Cl CH₃ H n-C₄H₉ CH₃ H H H 0 526 75 NO₂ H CN CN CH₃ Hn-C₄H₉ CH₃ H H H 0 600 76 NO₂ H CN NO₂ CH₃ H n-C₄H₉ CH₃ H H H 0 590 77NO₂ H Br CN CH₃ H n-C₄H₉ CH₃ H H H 0 562 78 NO₂ H Cl H CH₃ H CH₂CH₃ CH₃H H H 0 524 79 NO₂ H Cl H H H CH₂CH₃ CH₃ H H H 0 512 80 NO₂ H Cl Cl H HCH₂CH₃ CH₃ H H H 0 440 81 NO₂ H Br Cl H H CH₂CH₃ CH₃ H H H 0 442 82 NO₂H Br Br H H CH₂CH₃ CH₃ H H H 0 440 83 NO₂ H H Br H H CH₂CH₃ CH₃ H H H 0508 84 NO₂ Cl H Cl H H CH₂CH₃ CH₃ H H H 0 512 85 NO₂ H Br Cl H H n-C₄H₉CH₃ H H H 0 444 86 NO₂ H Cl Cl H H CH₂C₆H₅ CH₃ H H H 0 432 87 NO₂ H BrCl H H CH₂C₆H₅ CH₃ H H H 0 434 88 NO₂ H Cl H H H CH₂C₆H₅ CH₃ H H H 0 50089 NO₂ H H CN H H CH₂C₆H₅ CH₃ H H H 0 526 90 NO₂ H H CF₃ H H CH₂C₆H₅ CH₃H H H 0 506 91 NO₂ H Br Br H H CH₂C₆H₅ CH₃ H H H 0 432 92 NO₂ H H Br H HCH₂C₆H₅ CH₃ H H H 0 498 93 NO₂ H Cl Cl H H CH₂CH₂C₆H₅ CH₃ H H H 0 440 94NO₂ H Br Cl H H CH₂CH₂C₆H₅ CH₃ H H H 0 442 95 NO₂ H Cl Cl H HCH₂CH₂OC₆H₅ CH₃ H H H 0 436 96 NO₂ H Br Cl H H CH₂CH₂OC₆H₅ CH₃ H H H 0432 97 NO₂ H H Cl H H CH₂CH₂OC₆H₅ CH₃ H H H 0 502 98 NO₂ H H CN H HCH₂CH₂OC₆H₅ CH₃ H H H 0 526 99 NO₂ H Cl Cl H H CH₂CH₂CN CH₃ H H H 0 424100 NO₂ H Br Br H H CH₂CH₂CN CH₃ H H H 0 422 101 NO₂ H Cl Cl CH₃ HCH₂CH₃ CH₃ H H H 0 462 102 NO₂ H Br Cl CH₃ H CH₂CH₃ CH₃ H H H 0 460 103NO₂ H Cl CN CH₃ H CH₂CH₃ CH₃ H H H 0 562 104 NO₂ H Br CN CH₃ H CH₂CH₃CH₃ H H H 0 560 105 NO₂ H CN CN CH₃ H CH₂CH₃ CH₃ H H H 0 596 106 NO₂ H HH CH₃ H CH₂CH₃ CH₃ H H H 0 500 107 NO₂ H H Br CH₃ H CH₂CH₃ CH₃ H H H 0522 108 NO₂ Cl H Cl CH₃ H CH₂CH₃ CH₃ H H H 0 524 109 H NO₂ H H CH₃ HCH₂CH₃ CH₃ H H H 0 452 110 NO₂ Cl Cl H H H CH₂C₆H₅ CH₃ H H H 0 500 111NO₂ H H H OH H CH₂CH₃ CH₃ H H H 0 494 112 NO₂ H H Cl OH H CH₂CH₃ CH₃ H HH 0 530 113 NO₂ H H CN OH H CH₂CH₃ CH₃ H H H 0 544 114 NO₂ H Cl Cl OH HCH₂CH₃ CH₃ H H H 0 486 115 NO₂ H H H Cl OC₆H₅ H CH₃ H H H 0 478 116 NO₂H H CN Cl OC₆H₅ H CH₃ H H H 0 524 117 NO₂ H H Cl Cl OC₆H₅ H CH₃ H H H 0498 118 NO₂ H Cl Cl Cl OC₆H₅ H CH₃ H H H 0 444 119 NO₂ H H H H Cl H CH₃H H H 0 450 120 NO₂ H H Cl H Cl H CH₃ H H H 0 472 121 NO₂ H H H H Cl HC₂H₅ H H H 0 450 122 NO₂ H H NO₂ NHCOCH₃ Cl H CH₃ H H H 0 520 123 NO₂ HH H NHCOCH₃ Cl H CH₃ H H H 0 486 124 NO₂ H Cl NO₂ NHCOCH₃ Cl H CH₃ H H H0 536 125 NO₂ H Cl H NHCOCH₃ Cl H CH₃ H H H 0 508 126 NO₂ H H CN NHCOCH₃Cl H CH₃ H H H 0 530 127 NO₂ H Br NO₂ NHCOCH₃ OCH₃ H CH₃ CH₃ H H 0 596128 NO₂ H Cl NO₂ NHCOCH₃ OCH₃ H CH₃ CH₃ H H 0 596 129 NO₂ H Cl NO₂NHCOCH₃ OCH₃ H CH₃ H CH₃ H 0 592 130 NO₂ H Cl NO₂ NHCOCH₃ OCH₃ H CH₃ H HH 1 601 131 NO₂ H Br NO₂ NHCOCH₃ OCH₃ H CH₃ H H H 1 600 132 NO₂ H H NO₂NHCOCH₃ OCH₃ H CH₃ H H H 1 582 133 NO₂ H Br CN NHCOCH₃ OCH₃ H CH₃ H H H1 630 134 NO₂ H Cl NO₂ NHCOCH₃ OCH₃ H CH₃ H H CH₃ 0 594 135 NO₂ H Br NO₂NHCOCH₃ OCH₃ H CH₃ H H CH₃ 0 594 136 NO₂ H H NO₂ NHCOCH₃ OCH₃ H CH₃ H HCH₃ 0 576 137 NO₂ H Cl NO₂ NHCOCH₃ OCH₃ H CH₃ H H C₆H₅ 0 594 138 NO₂ HBr NO₂ NHCOCH₃ OCH₃ H CH₃ H H C₆H₅ 0 594 139 NO₂ H H NO₂ NHCOCH₃ OCH₃ HCH₃ H H C₆H₅ 0 576 140 NO₂ H Br NO₂ NHCOCH₃ CH₃ H CH₃ H H H 0 558 141NO₂ H Cl NO₂ NHCOCH₃ CH₃ H CH₃ H H H 0 558 142 NO₂ H Cl H NHCOCH₃ CH₃ HCH₃ H H H 0 532 143 NO₂ H Br CN NHCOCH₃ CH₃ H CH₃ H H H 0 584 144 NO₂ HH NO₂ NHCOCH₃ CH₃ H CH₃ H H H 0 538 145 CH₃ H CN CN NHCOCH₃ H CH₂CH₃ CH₃H H H 0 532

EXAMPLE 146

4.3 g of 3-amino-5-nitrobenzisothiazole are introduced into a mixture of11 ml of sulfuric acid (96%) and 4 ml of phosphoric acid (85%). Then,4.6 ml of nitrosylsulfuric acid (40%) are added dropwise at 10 to 15° C.The mixture is subsequently stirred at 10 to 15° C. for 4 hours. Thediazonium salt solution thus obtained is speedily added dropwise to amixture of 6.6 g of 2-oxopropyl3-[(5-acetylaminophenyl)ethylamino]-propionate, 100 ml of methanol, 1.1g of urea and 100 g of ice. The mixture is stirred at room temperatureovernight and the precipitate is filtered off with suction, washed with1:1 methanol/water and dried to leave 7.9 g of the dye of the formula(Ibb)

(λ_(max) [DMF]=622 nm), which dyes polyester in greenish blue shades andhas very good wash and sublimation fastnesses.

Examples 147 to 173 of Table 2 were prepared in a similar manner.

TABLE 2

Exam- λ_(max) ple D R¹ R² R³ R⁵ [DMF] 147

NHCOCH₃ OCH₃ H CH₃ 648 148

H H CH₂CH₃ CH₃ 606 149

H H CH₂C₆H₅ CH₃ 594 150

CH₃ H CH₂CH₃ CH₃ 618 151

H H CH₂CH₃ CH₃ 622 152

CH₃ H CH₂CH₃ CH₃ 636 153

CH₃ H CH₂CH₃ CH₃ 562 154

H H CH₂CH₃ CH₃ 550 155

H H CH₂C₆H₅ CH₃ 540 156

NHCOCH₃ H CH₂CH₃ CH₃ 564 157

CH₃ H CH₂CH₃ CH₃ 540 158

H H CH₂CH₃ CH₃ 530 159

NHCOCH₃ H CH₂CH₃ CH₃ 542 160

NHCOCH₃ H CH₂CH₃ CH₃ 596 161

NHCOCH₃ OCH₃ H CH₃ 608 162

NHCOCH₃ H CH₂CH₃ CH₃ 556 163

NHCOCH₃ H CH₂CH₃ CH₃ 526 164

NHCOCH₃ H CH₂C₆H₅ CH₃ 520 165

CH₃ H CH₂CH₃ CH₃ 520 166

NHCOCH₃ H CH₂CH₃ CH₃ 644 167

CH₃ H CH₂CH₃ CH₃ 668 168

H H CH₂CH₃ CH₃ 650 169

NHCOCH₃ H CH₂CH₃ CH₃ 604 170

CH₃ H CH₂CH₃ CH₃ 607 171

H H CH₂CH₃ CH₃ 592 172

NHCOCH₃ OCH₃ CH₂CH₃ CH₃ 650 173

H H CH₂CH₃ CH₃ 664

EXAMPLE 174

A textile fabric consisting of polyester is padded with a liquorconsisting of 50 g/l of 8% sodium alginate solution, 100 g/l of 8-12%carob flour ether solution and 5 g/l of monosodium phosphate in waterand then dried. The wet pickup is 70%.

The textile thus pretreated is then printed with an aqueous ink preparedin accordance with the procedure described above and containing

-   3.5% of the dye of Example 1,-   2.5% of Disperbyk 190 dispersant,-   30% of 1,5-pentanediol,-   5% of diethylene glycol monomethyl ether,-   0.01% of Mergal K9N biocide, and-   58.99% of water    using a drop-on-demand (piezo) ink jet print head. The print is    fully dried. Fixing is effected by means of superheated steam at    175° C. for 7 minutes. The print is subsequently subjected to an    alkaline reduction clear, rinsed warm and then dried.

1. A dye of the formula (I)

where D is the radical of a diazo component; R¹ is hydrogen,(C₁-C₆)-alkyl, (C₁-C₄)-alkoxy, hydroxyl, halogen, —NHCHO,—NHCO(C₁-C₆)-alkyl, —NHCOaryl, —NHSO₂(C₁-C₆)-alkyl or —NHSO₂aryl; R² ishydrogen, (C₁-C₆)-alkyl, (C₁-C₄)-alkoxy, phenoxy or halogen; R³ ishydrogen, (C₁-C₆)-alkyl, substituted (C₁-C₆)-alkyl, (C₃-C₄)-alkenyl orsubstituted (C₃-C₄)-alkenyl; or R² and R³ combine to form the radical—C*H(CH₃)CH₂C(CH₃)₂—, where the carbon atom marked by * is attached tothe phenyl nucleus; R⁴ is hydrogen, (C₁-C₆)-alkyl or phenyl; R⁵ is(C₁-C₆)-alkyl or substituted (C₁-C₆)-alkyl; R⁶ is hydrogen or(C₁-C₆)-alkyl; R⁷ is hydrogen, (C₁-C₆)-alkyl or phenyl; and n 0, 1, 2 or3; although the compounds of the formulae

shall be excluded.
 2. The dye as claimed in claim 1, wherein Drepresents a group of the formula (IIa)

where T¹ and T² independently are hydrogen, (C₁-C₆)-alkyl,(C₁-C₄)-alkoxy, —SO₂(C₁-C₆)-alkyl, —SO₂aryl, cyano, halogen or nitro;and T⁴ and T³ independently are hydrogen, halogen, trifluoromethyl,cyano, —SCN, —SO₂CH₃ or nitro; although at least one of T¹, T², T³ andT⁴ is not hydrogen; or represents a group of the formula (IIb)

where T⁵ and T^(5′) independently are hydrogen or halogen; and T⁶ ishydrogen, —SO₂CH₃, —SCN, (C₁-C₄)-alkoxy, halogen or nitro; although atleast one of T⁵, T^(5′) and T⁶ is not hydrogen; or represents a group ofthe formula (IIc)

where T¹² is hydrogen or halogen; or represents a group of the formula(IId)

where T⁷ is nitro, —CHO, cyano, —COCH₃ or a group of the formula

where T¹⁰ is hydrogen, halogen, nitro or cyano; T⁸ is hydrogen,(C₁-C₆)-alkyl or halogen; and T⁹ is nitro, cyano, —COCH₃ or —COOT¹¹;where T¹¹ is (C₁-C₄)-alkyl; or represents a group of the formula (IIe)

where T⁷ and T⁸ are each as defined above; or represents a group of theformula (IIf)

where T¹³ is phenyl or S—(C₁-C₄)-alkyl.
 3. The dye as claimed in claim1, wherein R¹ is hydrogen, chlorine, methyl, ethyl, methoxy, hydroxyl,ethoxy, acetylamino, propionylamino, benzoylamino, methylsulfonylamino,ethylsulfonylamino or phenylsulfonylamino; R² is hydrogen, chlorine,methyl, ethyl, methoxy, ethoxy or phenoxy; R³ is hydrogen, methyl,ethyl, propyl, butyl, benzyl, phenylethyl, phenoxyethyl, methoxyethyl,cyanoethyl, —C₂H₄OCOCH₃, —C₂H₄OCOC₂H₅, —C₂H₄COOCH₃, —C₂H₄COOC₂H₅ orallyl; R⁴ and R⁷ are hydrogen, methyl or phenyl; R⁵ is methyl or ethyl;R⁶ is hydrogen or methyl; and n is 0 or 1; although the compounds of theformulae

shall be excluded.
 4. The dye as claimed in claim 2, wherein R¹ ishydrogen, chlorine, methyl, ethyl, methoxy, hydroxyl, ethoxy,acetylamino, propionylamino, benzoylamino, methylsulfonylamino,ethylsulfonylamino or phenylsulfonylamino; R² is hydrogen, chlorine,methyl, ethyl, methoxy, ethoxy or phenoxy; R³ is hydrogen, methyl,ethyl, propyl, butyl, benzyl, phenylethyl, phenoxyethyl, methoxyethyl,cyanoethyl, —C₂H₄OCOCH₃, —C₂H₄OCOC₂H₅, —C₂H₄COOCH₃, —C₂H₄COOC₂H₅ orallyl; R⁴ and R⁷ are hydrogen, methyl or phenyl; R⁵ is methyl or ethyl;R⁶ is hydrogen or methyl; and n is 0 or 1; although the compounds of theformulae

shall be excluded.
 5. The dye according to claim 1, conforming to theformula (Ia)

where T¹ to T⁴, R¹ to R⁷ and n are each as defined in claim 1, althoughthe compounds of the formulae

shall be excluded.
 6. The dye as claimed in claim 5, wherein R¹ isacetylamino, propionylamino, benzoylamino or methylsulfonylamino; R² ishydrogen, chlorine, methoxy or ethoxy; R³ is hydrogen, methyl, ethyl,allyl or benzyl; R⁴ is hydrogen or methyl; R⁵ methyl or ethyl; R⁶ ishydrogen or methyl and R⁷ is hydrogen, methyl or phenyl.
 7. The dye asclaimed in claim 5, conforming to the formula (Iaa)

where T¹ is hydrogen, nitro or methyl; T² is hydrogen, nitro orchlorine; T³ is hydrogen, cyano, chlorine or bromine; T⁴ is hydrogen,cyano, nitro, chlorine, bromine or trifluoromethyl; R¹ is hydrogen,hydroxyl, chlorine, methyl, acetylamino, propionylamino, benzoylamino ormethylsulfonylamino; R² is hydrogen, chlorine, methyl, phenoxy, methoxyor ethoxy; R³ is hydrogen, methyl, ethyl, butyl, benzyl, phenylethyl,phenoxyethyl or allyl; R⁵ is methyl or ethyl; and R⁴ and R⁷ arehydrogen, methyl or phenyl; although the compounds of the formulae

shall be excluded.
 8. The dye as claimed in claim 7, wherein T³ ischlorine or bromine and R¹ is hydrogen or methyl.
 9. A process forpreparing a dye of the formula (I) as claimed in claim 1, whichcomprises diazoting a compound of the formula (III)D-NH₂  (III) where D is as defined in claim 1, and coupling onto acompound of the formula (IV)

where R¹ to R⁷ and n are each as defined in claim
 1. 10. A process fordyeing and printing a hydrophobic material which comprises contactingthe material with the dye as claimed in claim
 1. 11. An ink for digitaltextile printing by the ink jet process, comprising the dye of theformula (I) as claimed in claim
 1. 12. An ink for digital textileprinting by the ink jet process, comprising the dye of the formula (I)as claimed in claim 8.